The invention relates to monomers of the general formula I with a reactive aromatic system based on p-phenylenediamine derivatives: EQU CH.sub.2 .dbd.CR.sup.1 --CO--(O--CH.sub.2 --CH.sub.2).sub.x --HR.sup.2 --Ar--NH--R.sup.3 (I),
where R.sup.1 is H or CH.sub.3, R.sup.2 is C.sub.1 -C.sub.6 alkyl, R.sup.3 is acyl, carboxylic group or sulfonic group. It further relates to methods for preparation of such monomers by the reaction of p-H.sub.2 NC.sub.6 H.sub.4 N(Et)CH.sub.2 CH.sub.2 OH or p-H.sub.2 NC.sub.6 H.sub.4 N(CH.sub.2 CH.sub.2 OH).sub.2 derivatives with blocked NH.sub.2 groups with chlorides of unsaturated organic acids or by nitrosation, reducing and above mentioned acylation of N-alkylaniline derivatives. If further relates to polymers prepared by polymerization or copolymerization of monomers I, which consist of structural units IV: ##STR2## where R.sup.1, R.sup.2, R.sup.3, Ar and x have the above given meaning, and to methods of their preparation. These methods include the free-radical polymerization or copolymerization with acrylic and methacrylic monomers, as acrylamide, methacrylamide. acrylic and methacrylic acids and their esters, vinyl monomers, as butadiene, isoprene, and styrene, bifunctional monomers, as divinylbenzene, methylenebisacrylamide, ethylene glycol dimethacrylate, and with monomers containing OH groups. The polymerization methods further include polymerization in the presence of polymer solvents and precipitants and a crosslinking copolymerization in a dispersion medium which provides porous polymer particles with large inner surface area. Another objective of the invention are polymers containing structural units V: ##STR3## where R.sup.1, R.sup.2, Ar and x have the above given meaning and R.sup.3, R.sup.4 are H, C.sub.1 -C.sub.4 alkyl or CH.sub.2 COOH or where R.sup.3 +R.sup.4 means=N-group, and methods for their preparation from polymers with units IV consisting in acid hydrolysis and subsequent modification, e.g. with chloroacetic acid, formaldehyde or diazotizing and coupling with a suitable passive component.
Efforts to prepare new kinds of polymers with built-in functional groups, which enable chemical modifications of the polymeric system, lead to syntheses of numerous compounds having the character of monomers. The invention relates to compounds chemically derived from p-phenylenediamine which contain an acrylic or methacrylic residue allowing their polymerization reaction, to synthetic polymers which contain in the side chain a p-phenylenediamine skeleton enabling manifold chemical modifications of the system, and to methods of their preparation. The aim is to prepare such monomers which enable preparation of materials suitable for subsequent application, e.g. as a catalyst of chemical reaction, biologically active preparation, ion exchanger, and the like, by a simple subsequent reaction of the polymer.
Interest in polymers with reactive functional groups, which are raw materials for numerous products of both technological and application importance, caused the rapid development of modified polymeric systems. These polymers are prepared by modification of the fundamental polymeric skeleton by a subsequent chemical reaction, on the one hand, and by copolymerization of suitable monomers with reactive groups capable of further reactions, on the other.
Polymers preformed in this way may be tranformed by further chemical conversions into materials useful for biological applications, technical applications, and the like.
They were developed materials containing an aliphatic or aromatic primary amino group in the side chain which may be used, for example, for further reactions of the bonding character via diazotizing of the aromatic amino group and the subsequent coupling with a suitable kind of substrate. However, most of these systems prefer the one-sided utilization. In addition to it, several reactions provide imperfectly defined products because the modification reactions are not quantitative or the corresponding comonomers have unsuitable reactivity ratios.
An objective of the invention are monomers containing p-phenylenediamine skeleton of the general formula I ##STR4## where R.sup.1 is hydrogen or methyl, R.sup.2 is alkyl containing 1 to 6 carbon atoms, R.sup.3 is an acyl or sulfonic group, Ar is a bifunctional aromatic residue, and x=1 to 4.
Monomers of the above given type may be prepared by reaction of chloride of an unsaturated organic acid (for example, acryloyl or methacryloyl chloride) with hydroxy derivative of p-phenylenediamine of the following types: ##STR5##
The above mentioned monomers may be also prepared in such way that ethoxylated derivatives of N-alkylaniline or aniline are synthesized and then nitrosated, reduced and subjected to the subsequent reaction with chloride of an unsaturated organic acid, e.g. acryloyl or methacryloyl chloride.
Numerous initial compounds may be employed in preparation of monomers, beginning with common compounds of phenylenediamine type, which are used e.g. in photographic chemistry, as far as to simple basic raw materials. While the first type of preparation from compounds ##STR6## requires, after previous blocking of the free primary amino group, e.g. by acylation (R.sup.3), only the reaction with acryloyl or methacryloyl chloride, the stepwise synthesis with the analogous end step must be chosen in other cases.
Monomers of this type are noted for their suitable copolymerisation reactivity ratios with common monomers. They can be prepared as mono- or bifunctional monomers at the same time and, consequently, used for preparation of linear polymers soluble in proper solvents or insoluble crosslinked polymers.
An objective of the invention are further polymers containing a reactive aromatic system in the side chain, which consist of structural units of the general formula IV: ##STR7## where R.sup.1 is hydrogen or methyl, R.sup.2 is alkyl containing 1 to 6 carbon atoms, R.sup.3 is an acyl, carboxylic or sulfonic group, Ar is a bifunctional aromatic residue, and x=1 to 4.
Polymers of the general formula IV are prepared by a free radical polymerization of the corresponding monomer in the presence of an initiator of free-radical polymerization at or above the decomposition temperature of the initiator.
As further comonomers, they may be advantageously used the monomers of methacrylic or acrylic series, for instance acrylamide, methacrylamide, acrylic acid, methacrylic acid, of their esters, and vinyl compounds, as butadiene, isoprene, styrene, and others.
The polymerization is advantageously carried out in the presence of polymer solvents and precipitants or in a dispersion medium under formation of porous polymer particles having large inner surface area.
The invention enables to prepare a polymeric system, the chemical reactivity of which given by the conjugated nitrogen system allows to perform several reactions leading to products with specific properties. With respect to advantageous copolymerization reactivity ratios, especially with acrylates and methacrylates, materials of the defined structure with high content of reactive groups may be prepared. The copolymers may be indeed prepared also with other types of monomers, as with styrene, divinylbenzene and their derivatives, isoprene, butadiene, and others.
The character of the reactive system prefers namely copolymerizations with monomers of hydrophilic nature, e.g. with esters containing hydroxyl group in the side chain, i.e. esters of glycols, polyglycols or glycerol, with amides, i.e. acrylamide, methacrylamide, or N-substituted acrylamides and methacrylamides, and naturally, with methacrylic and acrylic acids.
The preparation of copolymers in the form of a three-dimensional network by copolymerization with multifunctional monomers, as for instance with divinylbenzene, ethylene glycol dimethacrylate or methylenebisacrylamide, leads to insoluble homogeneous or heterogeneous copolymers. In the presence of a suitable solvent system, polymers with large inner surface area and porosity are formed, which properties predetermine these materials for broad application, namely those prepared in the form of small spherical particles for chromatographic and catalytic purposes and for ion exchange.
Polymers preformed in this way may be transformed by further chemical conversions into materials useful for biological and technical applications, and the like.
Another objective of the invention are polymers containing a reactive aromatic system in the side chain, which consist of structural units of the general formula V: ##STR8## where R.sup.1 is hydrogen or methyl, R.sup.2 is alkyl containing 1 to 6 carbon atoms, R.sup.3 and R.sup.4 are hydrogen, alkyl containing 1 to 4 carbon atoms or --CH.sub.2 COOH group, or R.sup.3 +R.sup.4 is the group .dbd.N--, Ar is a bifunctional aromatic residue, and x=1 to 4.
Polymers according to this invention may be prepared by subjecting the polymer of the general formula IV ##STR9## where R.sup.1 is hydrogen or methyl, R.sup.2 is alkyl containing 1 to 6 carbon atoms, R.sup.3 is an acyl, carboxylic or sulfonic group, Ar is a bifunctional aromatic residue, and x=1 to 4, to acid hydrolysis and modification of the resulting product.
The reactive site is, for example, a primary aromatic amino group which may be diazotized and used in coupling reactions with various components.
Alkylation of the primary amino group carried out, for example, by reaction with formaldehyde (see Example 9) leads to aromatic tertiary alkylamine built into the polymeric skeleton.
Another example consists in formation of a polymeric derivative of aminodiacetic acid by reaction of the polymer with choroacetic acid.
Polymers according to the invention may be advantageously used as ion exchangers, catalysts of chemical reactions, for biological applications, etc.
Synthesis of monomers and polymers containing the p-phenylenediamine skeleton is further illustrated in example of performance without, however, limiting the scope of this invention to these examples.